EP1977041A1 - A composition for surface colouration of paper - Google Patents

A composition for surface colouration of paper

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Publication number
EP1977041A1
EP1977041A1 EP20070703929 EP07703929A EP1977041A1 EP 1977041 A1 EP1977041 A1 EP 1977041A1 EP 20070703929 EP20070703929 EP 20070703929 EP 07703929 A EP07703929 A EP 07703929A EP 1977041 A1 EP1977041 A1 EP 1977041A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
starch
pigment
total weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20070703929
Other languages
German (de)
French (fr)
Other versions
EP1977041B1 (en
Inventor
Michael Lennartz
Charles Hunger
Asko Olavi Karppi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
Ciba Holding AG
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Filing date
Publication date
Application filed by Ciba Holding AG filed Critical Ciba Holding AG
Priority to EP20070703929 priority Critical patent/EP1977041B1/en
Publication of EP1977041A1 publication Critical patent/EP1977041A1/en
Application granted granted Critical
Publication of EP1977041B1 publication Critical patent/EP1977041B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a composition for surface colouration of paper web comprising a colouring pigment, a synthetic starch/latex copolymer and, optionally, further additives and the use thereof for surface colouration of said paper web.
  • a dye composition containing a binder and thickener which is a polyvinylpyrrolidone derivative
  • a dye composition containing a binder and thickener which is a polyvinylpyrrolidone derivative
  • the paper surface is treated with a fixing agent prior to the dyeing process in order to improve bleed fastness, but no concrete values are given to indicate the effectiveness of this approach.
  • WO 04/090228 discloses a composition for controlling the bleed fastness of organic colouring pigments in paper coatings comprising a colouring pigment and, essentially, a binder.
  • Suitable binders are selected from an extremely wide variety of entities, but most preferred and efficient are binders based on copolymers of starch with styrene/butadiene latex.
  • relatively high quantities of binder are required to achieve the desired bleed fastness and it has also been observed that the resulting dyeings lack sufficiently high quality for certain applications, due to, for example, excessive mottling and lack of homogeneity.
  • compositions comprising colouring pigments and particular starch based copolymer binders result in dyeings which, in addition to exhibiting excellent bleed fastness at relatively low application concentrations, are of exceptionally high quality, in particular, with respect to mottling, colour strength and homogeneity.
  • a composition comprising a) from 0.1 to 30%, preferably from 1 to 25%, by weight, based on the total weight of the composition, of a colouring pigment, b) from 0.1 to 20%, preferably from 0.5 to 10% and most preferably from 1 to 5%, by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally , iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20%, preferably from 0 to 10%, by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to complete
  • component a) of the composition may be selected from any colouring pigment as described in the Colour Index International, fourth online edition (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) under the designations C.I. Pigment Yellows 1 to 221 , C.I. Pigment Oranges 1 to 81 , C.I. Pigment Reds 1 to 283, C.I. Pigment Violets 1 to 53, C.I. Pigment Blues 1 to 81 , C.I. Pigment Greens 1 to 56, C.I. Pigment Browns 1 to 47 and C.I. Pigment Blacks 1 to 35.
  • any colouring pigment as described in the Colour Index International, fourth online edition (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) under the designations C.I. Pigment Yellows 1 to 221 , C.I. Pigment Oranges 1 to 81 , C.I. Pigment Reds 1 to 283, C.I. Pigment Violet
  • the colouring pigment is selected from C.I. Pigment Yellow 1 , 3, 12, 13, 14, 17, 34, 42, 51 , 53, 62, 74, 83, 93, 95, 109, 110, 11 1 , 128, 129, 139, 147, 168, 174, 184, 188, 191 :1 and 199, C.I. Pigment Orange 5, 13, 16, 23, 34, 49, 61 , 63, 64, 71 , 73, and 81 , C.I.
  • the ratios of starch to unsaturated monomers for the preparation of the starch/latex copolymer, component b) of the composition generally lie within the range of i) from 5 to 50%, preferably from 5 and 40%, by weight of starch and ii) from 50 to 95%, preferably from 60 to 95%, by weight of the monomeric components, whereby the copolymers may advantageously be utilized in the form of aqueous dispersions.
  • These polymer dispersions generally contain between 20 and 50%, preferably between 25 and 35%, dry weight of solids.
  • Polymerisable starch or starch derivatives suitable for incorporating into component b) and also as the optional component c) of the composition of the invention may include practically all thinned starches of plant origin including starches from corn, wheat, potatoes, tapioca, rice, sago and sorghum. Waxy and high amylose starches may also be suitable. The starches can be thinned by acid hydrolysis, oxidative hydrolysis or enzymatic degradation. Further derivatized starches also suitable include those such as starch ethers, starch esters, cross-linked starches, oxidized starches and chlorinated starches, for example, carboxymethyl cellulose and hydroxyethyl methyl cellulose. Typical examples are the commercially available amylopectin, dextrin and, as a typical example of oxidized starch, Perfectamyl® 4692.
  • component b) of the composition of the invention is preferably obtained by copolymerization of a degraded, oxidized anionic starch.
  • component b) of the composition of the invention In addition to the starch component of the copolymer, component b) of the composition of the invention, the individual monomers and their relative amounts are critical for providing the advantageous properties provided by the invention.
  • the starch/latex copolymer, component b) of the composition of the invention is obtained, preferably by emulsion polymerization of a mixture of monomers consisting of i) from 20 to 40% by weight of styrene or a substituted styrene, ii) from 20 to 50% of an acrylate or a methacrylate and - A -
  • Substituted styrenes may include, for example, ⁇ -methyl styrene, or styrenes substituted in the phenyl ring by alkyl groups, such as methyl, halogens, such as chlorine or alkoxy groups such as methoxy.
  • alkyl groups such as methyl
  • halogens such as chlorine or alkoxy groups such as methoxy.
  • styrene itself is the most preferred component.
  • Acrylates or methacrylates are preferably lower alkyl esters such as methyl, ethyl, n- or isopropyl and n-, iso-, sec- or tert-butyl esters or their mixtures, n-butyl acrylate being the most preferred component.
  • this may be selected from a wide variety of compounds containing one single unsaturated double bond, i.e. excluding dienes of previously disclosed starch/latex copolymers such as 1 ,3-butadiene or isoprene.
  • Suitable ethylenically unsaturated monomers are hydroxylated alkyl methacrylates, alkyl vinyl ketones, substituted acrylamides, methacrylic acid, N-methylol acrylamide, 2- hydroxyethyl acrylate, crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, vinyl halides, vinylidene halides, vinyl esters, vinyl ethers, vinyl carbazole, N-vinyl pyrrolidone, vinyl pyridine, ethylene, propylene, isobutylene, vinyl triethoxy silane and triphenyl vinyl silane.
  • Preferred monomers include dimethylamino ethyl acrylate, dimethylamino propyl acrylamide, vinyl acetate, acrylic acid, acrylamide, maleic anhydride, monovinyl silicon compounds including vinyl trimethyl silane, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl acrylate vinylidine chloride, butyl vinyl ether and, especially acrylonitrile.
  • the starch/latex copolymer, component b) of the composition of the invention is a product obtained by emulsion polymerization of i) from 20 to 40% by weight of styrene, ii) from 20 to 50% by weight of a Ci-C 4 alkylacrylate, especially n-butyl acrylate and iii) from 5 to 20% by weight of vinyl acetate or, especially, acrylonitrile, in the presence of from 15 to 35% by weight of an oxidatively degraded anionic starch, in the form of an aqueous dispersion having a dry content of between 25 and 35% by weight.
  • composition of the invention may contain further auxiliaries selected from fixing agents, dispersants, additional binder and binder resins, insolubilizing and/or crosslinking agents, anionic, cationic and neutral polymers, wet-strength agents, antifoams and biocides.
  • Suitable auxiliaries may, for example, include polyethyleneimines and derivatives thereof, inorganic salts such as sodium chloride, magnesium chloride and potassium chloride, alum, polydiallyl dimethyl ammonium chloride, polyamide amine resins, polyvinyl alcohol, polyvinyl pyrrolidone and homo and copolymers thereof, polyesters and polyethers, glyoxal derivatives, monoethanolamine, acrylic acid/alkyl acrylate copolymers and styrene/acrylate copolymers.
  • inorganic salts such as sodium chloride, magnesium chloride and potassium chloride
  • alum polydiallyl dimethyl ammonium chloride
  • polyamide amine resins polyamide amine resins
  • polyvinyl alcohol polyvinyl pyrrolidone and homo and copolymers thereof
  • polyesters and polyethers glyoxal derivatives
  • monoethanolamine acrylic acid/alkyl acrylate copolymers
  • composition of the invention is suitable for use in surface colouration of paper web after sheet formation.
  • the composition is applied to the paper web after it has been dried to 80 to 95% in the size press or by means of an on-line coater.
  • the composition can be applied once the paper has been fully dried in an off-machine coating process, such as by spraying, curtain coating or by conventional coating processes.
  • the invention relates to a method for the surface colouration of paper by applying to the paper surface a composition
  • a composition comprising a) from 0.1 to 30% by weight, based on the total weight of the composition, of a colouring pigment, whereby the colouring pigment is in solid form or in the form of a dispersion, in which form many colouring pigments are commercially available, b) from 0.1 to 20% by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch, the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally, iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20% by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to
  • the pigment is used in the form of a dispersion
  • addition of the starch/latex copolymer generally suffices to achieve the desired effect, i.e. bleed fastness of the resulting dyed paper web, without addition of further starch binder, component c) of the composition, which is clearly advantageous.
  • compositions comprising colouring pigments and particular starch based copolymer binders result in dyeings exhibiting excellent bleed fastness at relatively low application concentrations and which are of exceptionally high quality, in particular, with respect to colour strength and homogeneity, including lack of mottling, as opposed to previously known combinations.
  • Base Paper The base paper used for the application was fabricated on a laboratory paper machine at UMIST, Manchester, UK from a 70/30 mixture of hard and soft woods pulp beaten to 35° SR, containing 10% retained clay (plus 1 % calcium carbonate) filler, 0.4% Hercat® 27JP4 pseudo neutral size, 1 % alum and 0.02% Percol® 230 retention agent. The resulting paper has a base weight of 103g/m 2 and a Cobb value of 95g/m 2 .
  • pigment and copolymer are added to 44g of a 10% aqueous solution of size press starch (Perfectamyl® 4692) and the mixture made up to 100g with water, where after the mixture is applied to the base paper in a Mathis size press running at 5m/min., with a pressure of 200kPas and at a temperature of 5O 0 C.
  • the bleed fastness of the dyeings towards water and 50% alcohol/water are measured by firstly moistening the dyeing with deionised water and alcohol/water respectively and placing the moist dyeings between two sheets of white filter papers which are moistened with deionised water and alcohol/water respectively.
  • the resulting sandwich is placed between two glass plates weighted with a 1 kg weight. After 1 hour at room temperature, the individual sheets are dried and the bleed fastness assessed by means of the grey scale, whereby a value between 1 (very strong bleeding) and 5 (zero bleeding) is obtained.
  • PF Bleed fastness between filter papers
  • GF Bleed fastness between glass fibre sheet
  • Polymer A is an experimental product obtained by emulsion copolymerization of 25% starch(Raisamyl® 01121 , oxidatively degraded anionic starch), 38.6% styrene, 28.6% n-butyl acrylate and 7.8% acrylonitrile;
  • Pensize® 730 is a commercially available aqueous formulation of a starch/styrene/ butadiene latex copolymer
  • Raiprint® 501 is a commercially available product obtained by copolymerization of 25% Raisamyl® 150 EH (a cationic starch), 38.62% styrene, 28.61 % n-butylacrylate and 7.76% acrylonitrile;
  • Raiprint® 300 is a commercially available product obtained by copolymerization of 20% Raisafix® 01015 SW (an amphoteric starch), 24.8% styrene, 40%n-butyl acrylate and 15.2% acrylonitrile.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention relates to a composition fur surface coloration of paper web comprising a) from 0.1 to 30% by weight, based on the total weight of the composition, of a colouring pigment, b) from 0.1 to 20% by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to stare ii, the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) acrylate and/or methacrylate and, optionally, iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20% by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to 100% by weight, based on the total weight of the composition.

Description

A Composition for Surface Colouration of Paper
The present invention relates to a composition for surface colouration of paper web comprising a colouring pigment, a synthetic starch/latex copolymer and, optionally, further additives and the use thereof for surface colouration of said paper web.
Despite the fact that the economical advantages of surface colouration of paper have long been recognized, in practice, surface colouration is not widespread when compared with stock dyeing. The main reason for this situation (see, for example, "On-machine surface coloration", A.S.Tindal, Surface Application of Paper Chemicals, 1997, 175-191 ) is that surface coloured paper generally exhibits poor bleed fastness when contacted with liquids such as water, alcohol or beverages.
One attempt to overcome this problem has been disclosed in WO 03/004766, whereby a dye composition containing a binder and thickener, which is a polyvinylpyrrolidone derivative, is applied to the paper surface. Preferably, the paper surface is treated with a fixing agent prior to the dyeing process in order to improve bleed fastness, but no concrete values are given to indicate the effectiveness of this approach.
A further approach to overcome the bleeding problems associated with surface colouration of paper has been disclosed in WO 04/090228. This document discloses a composition for controlling the bleed fastness of organic colouring pigments in paper coatings comprising a colouring pigment and, essentially, a binder. Suitable binders are selected from an extremely wide variety of entities, but most preferred and efficient are binders based on copolymers of starch with styrene/butadiene latex. However, relatively high quantities of binder are required to achieve the desired bleed fastness and it has also been observed that the resulting dyeings lack sufficiently high quality for certain applications, due to, for example, excessive mottling and lack of homogeneity.
Consequently, there is a need for a system for surface colouration of paper in which the disadvantages of previous compositions are overcome.
It has now been found that compositions comprising colouring pigments and particular starch based copolymer binders result in dyeings which, in addition to exhibiting excellent bleed fastness at relatively low application concentrations, are of exceptionally high quality, in particular, with respect to mottling, colour strength and homogeneity.
Therefore, a composition comprising a) from 0.1 to 30%, preferably from 1 to 25%, by weight, based on the total weight of the composition, of a colouring pigment, b) from 0.1 to 20%, preferably from 0.5 to 10% and most preferably from 1 to 5%, by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally , iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20%, preferably from 0 to 10%, by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to 100% by weight, based on the total weight of the composition has been found.
With regard to the colouring pigment, component a) of the composition, this may be selected from any colouring pigment as described in the Colour Index International, fourth online edition (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) under the designations C.I. Pigment Yellows 1 to 221 , C.I. Pigment Oranges 1 to 81 , C.I. Pigment Reds 1 to 283, C.I. Pigment Violets 1 to 53, C.I. Pigment Blues 1 to 81 , C.I. Pigment Greens 1 to 56, C.I. Pigment Browns 1 to 47 and C.I. Pigment Blacks 1 to 35.
Preferably, the colouring pigment is selected from C.I. Pigment Yellow 1 , 3, 12, 13, 14, 17, 34, 42, 51 , 53, 62, 74, 83, 93, 95, 109, 110, 11 1 , 128, 129, 139, 147, 168, 174, 184, 188, 191 :1 and 199, C.I. Pigment Orange 5, 13, 16, 23, 34, 49, 61 , 63, 64, 71 , 73, and 81 , C.I. Pigment Red 2, 4, 5, 12, 23, 38, 48:1 , 48:2, 48:3, 48:4, 49:1 , 52:2, 53:1 , 57, 57:1 , 81 , 101 , 104, 1 10, 112, 144, 146, 166, 177, 181 , 184, 185, 202, 206, 214, 220, 221 , 254, 255, 264, 270, 272, 282 and 283, C.I. Pigment Violet 3, 19, 23, and 37, C.I. Pigment Blue 1 , 15, 15:1 , 15:2, 15:3, 15:4, 29, 60 and 66, C.I. Pigment Green 60 and 66, C.I. Pigment Brown 23 and 24 and from C.I. Pigment Black 7, 10 and 34. The ratios of starch to unsaturated monomers for the preparation of the starch/latex copolymer, component b) of the composition, generally lie within the range of i) from 5 to 50%, preferably from 5 and 40%, by weight of starch and ii) from 50 to 95%, preferably from 60 to 95%, by weight of the monomeric components, whereby the copolymers may advantageously be utilized in the form of aqueous dispersions. These polymer dispersions generally contain between 20 and 50%, preferably between 25 and 35%, dry weight of solids.
Aqueous dispersions of similar copolymers have been described in WO 00/46264, which document also discloses a process for their preparation.
Polymerisable starch or starch derivatives suitable for incorporating into component b) and also as the optional component c) of the composition of the invention may include practically all thinned starches of plant origin including starches from corn, wheat, potatoes, tapioca, rice, sago and sorghum. Waxy and high amylose starches may also be suitable. The starches can be thinned by acid hydrolysis, oxidative hydrolysis or enzymatic degradation. Further derivatized starches also suitable include those such as starch ethers, starch esters, cross-linked starches, oxidized starches and chlorinated starches, for example, carboxymethyl cellulose and hydroxyethyl methyl cellulose. Typical examples are the commercially available amylopectin, dextrin and, as a typical example of oxidized starch, Perfectamyl® 4692.
However, component b) of the composition of the invention is preferably obtained by copolymerization of a degraded, oxidized anionic starch.
In addition to the starch component of the copolymer, component b) of the composition of the invention, the individual monomers and their relative amounts are critical for providing the advantageous properties provided by the invention.
Thus, in a further preferred aspect, the starch/latex copolymer, component b) of the composition of the invention, is obtained, preferably by emulsion polymerization of a mixture of monomers consisting of i) from 20 to 40% by weight of styrene or a substituted styrene, ii) from 20 to 50% of an acrylate or a methacrylate and - A -
iii) from 5 to 20% by weight of one or more further ethylenically unsaturated monomers in the presence of from 15 to 40%, preferably from 15 to 35%, by weight of starch,
Substituted styrenes may include, for example, α-methyl styrene, or styrenes substituted in the phenyl ring by alkyl groups, such as methyl, halogens, such as chlorine or alkoxy groups such as methoxy. However, styrene itself is the most preferred component.
Acrylates or methacrylates are preferably lower alkyl esters such as methyl, ethyl, n- or isopropyl and n-, iso-, sec- or tert-butyl esters or their mixtures, n-butyl acrylate being the most preferred component.
With regard to the third ethylenically unsaturated monomer, this may be selected from a wide variety of compounds containing one single unsaturated double bond, i.e. excluding dienes of previously disclosed starch/latex copolymers such as 1 ,3-butadiene or isoprene. Examples of suitable ethylenically unsaturated monomers are hydroxylated alkyl methacrylates, alkyl vinyl ketones, substituted acrylamides, methacrylic acid, N-methylol acrylamide, 2- hydroxyethyl acrylate, crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, vinyl halides, vinylidene halides, vinyl esters, vinyl ethers, vinyl carbazole, N-vinyl pyrrolidone, vinyl pyridine, ethylene, propylene, isobutylene, vinyl triethoxy silane and triphenyl vinyl silane. Preferred monomers include dimethylamino ethyl acrylate, dimethylamino propyl acrylamide, vinyl acetate, acrylic acid, acrylamide, maleic anhydride, monovinyl silicon compounds including vinyl trimethyl silane, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl acrylate vinylidine chloride, butyl vinyl ether and, especially acrylonitrile.
In a most preferred aspect, the starch/latex copolymer, component b) of the composition of the invention is a product obtained by emulsion polymerization of i) from 20 to 40% by weight of styrene, ii) from 20 to 50% by weight of a Ci-C4alkylacrylate, especially n-butyl acrylate and iii) from 5 to 20% by weight of vinyl acetate or, especially, acrylonitrile, in the presence of from 15 to 35% by weight of an oxidatively degraded anionic starch, in the form of an aqueous dispersion having a dry content of between 25 and 35% by weight.
Furthermore, the composition of the invention may contain further auxiliaries selected from fixing agents, dispersants, additional binder and binder resins, insolubilizing and/or crosslinking agents, anionic, cationic and neutral polymers, wet-strength agents, antifoams and biocides.
Suitable auxiliaries may, for example, include polyethyleneimines and derivatives thereof, inorganic salts such as sodium chloride, magnesium chloride and potassium chloride, alum, polydiallyl dimethyl ammonium chloride, polyamide amine resins, polyvinyl alcohol, polyvinyl pyrrolidone and homo and copolymers thereof, polyesters and polyethers, glyoxal derivatives, monoethanolamine, acrylic acid/alkyl acrylate copolymers and styrene/acrylate copolymers.
The composition of the invention is suitable for use in surface colouration of paper web after sheet formation.
Preferably, the composition is applied to the paper web after it has been dried to 80 to 95% in the size press or by means of an on-line coater. Alternatively, the composition can be applied once the paper has been fully dried in an off-machine coating process, such as by spraying, curtain coating or by conventional coating processes.
Such application processes are described in "Pigment Coating and Surface Sizing of Papers" by E.Lehtinen, published by Tappi International, 2000.
Consequently, in a still further aspect, the invention relates to a method for the surface colouration of paper by applying to the paper surface a composition comprising a) from 0.1 to 30% by weight, based on the total weight of the composition, of a colouring pigment, whereby the colouring pigment is in solid form or in the form of a dispersion, in which form many colouring pigments are commercially available, b) from 0.1 to 20% by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch, the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally, iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20% by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to 100% by weight, based on the total weight of the composition and also to paper, which has been treated with a composition of the invention or according to the method above.
Where, in the above method, the pigment is used in the form of a dispersion, addition of the starch/latex copolymer generally suffices to achieve the desired effect, i.e. bleed fastness of the resulting dyed paper web, without addition of further starch binder, component c) of the composition, which is clearly advantageous.
The inventive compositions comprising colouring pigments and particular starch based copolymer binders result in dyeings exhibiting excellent bleed fastness at relatively low application concentrations and which are of exceptionally high quality, in particular, with respect to colour strength and homogeneity, including lack of mottling, as opposed to previously known combinations.
The following examples further illustrate the invention, without intending to be restrictive in nature; parts and percentages are by weight unless otherwise indicated.
Examples
I. Size Press Application
Base Paper: The base paper used for the application was fabricated on a laboratory paper machine at UMIST, Manchester, UK from a 70/30 mixture of hard and soft woods pulp beaten to 35° SR, containing 10% retained clay (plus 1 % calcium carbonate) filler, 0.4% Hercat® 27JP4 pseudo neutral size, 1 % alum and 0.02% Percol® 230 retention agent. The resulting paper has a base weight of 103g/m2 and a Cobb value of 95g/m2.
Application:
Defined amounts of pigment and copolymer (see Table 1 ) are added to 44g of a 10% aqueous solution of size press starch (Perfectamyl® 4692) and the mixture made up to 100g with water, where after the mixture is applied to the base paper in a Mathis size press running at 5m/min., with a pressure of 200kPas and at a temperature of 5O0C.
After drying, the resulting colour strengths of the dyeings are then measured, whereby the values given in Tables 1 and 2 are corrected, taking the reference dyeing without copolymer addition as standard (100%), to take into account the amount of colorant actually residing on the paper surface. The absolute measured values of colour strength are given in parentheses.
Additionally, the bleed fastness of the dyeings towards water and 50% alcohol/water are measured by firstly moistening the dyeing with deionised water and alcohol/water respectively and placing the moist dyeings between two sheets of white filter papers which are moistened with deionised water and alcohol/water respectively. The resulting sandwich is placed between two glass plates weighted with a 1 kg weight. After 1 hour at room temperature, the individual sheets are dried and the bleed fastness assessed by means of the grey scale, whereby a value between 1 (very strong bleeding) and 5 (zero bleeding) is obtained.
The results of the measurements are summarized in the following Table 1 :
PF = Bleed fastness between filter papers; GF = Bleed fastness between glass fibre sheet
3 Polymer A is an experimental product obtained by emulsion copolymerization of 25% starch(Raisamyl® 01121 , oxidatively degraded anionic starch), 38.6% styrene, 28.6% n-butyl acrylate and 7.8% acrylonitrile;
4 Pensize® 730 is a commercially available aqueous formulation of a starch/styrene/ butadiene latex copolymer;
5 Raiprint® 501 is a commercially available product obtained by copolymerization of 25% Raisamyl® 150 EH (a cationic starch), 38.62% styrene, 28.61 % n-butylacrylate and 7.76% acrylonitrile;
6 Raiprint® 300 is a commercially available product obtained by copolymerization of 20% Raisafix® 01015 SW (an amphoteric starch), 24.8% styrene, 40%n-butyl acrylate and 15.2% acrylonitrile.
From the above Table 1 , the advantages of the experimental Polymer A over the commercial product Pensize 730 are clearly visible. Thus, for example, taking into account the pick-up from the size press bath, it may be calculated that in order to obtain acceptable bleed fastness of 4-5 minimum at comparable depth of colour, with C.I. Pigment Violet 23, 2.22% of Polymer A is required, whilst 4.57% Pensize 730 must be applied. Similar comparisons for C.I. Pigment Blue 15.1 and C.I. Pigment Red 2 result in values of 0.83% as opposed to 5.0% and 0.98% as opposed to 3.58%, respectively.
In addition, the superior efficiency of the experimental polymer A, in general, demonstrates the advantages of this copolymer in comparison to the commercially available Raiprint® products.
Also of note are the results obtained with C.I. Pigment Black 7, whereby solely Polymer A can be seen to produce dyeings of adequate colour strength. In a further series of experiments, dyeings of the dark shades, violet, blue and red, were examined in greater detail. The results are summarized in the following Table 2:
to , see footnotes at end of Table 1
As in the previous experiments, the quantities of Polymer A required for producing dyeings of acceptable bleed fastness and depth of colour are considerably lower than the quantities of Pensize 730. Thus for example, in the case of C.I. Pigment Violet 23, 0.96% of Polymer A is required, whilst 4.26% of Pensize 730 is necessary. Analogous values with C.I. Pigment Blue 15:1 are 0.73% as opposed to above 3.84% and for C.I. Pigment Red 2, 0.41 % as opposed to 3.71 % Pensize 730.
Once again, the poor performance of the Pensize® 730 series in terms of color strength and dyeing efficiency is apparent when small or medium amounts of this copolymer are employed.
In one further series of experiments, not only the quantities of copolymer, but also the quantities of pigment were varied. The colour strengths in the Table represent the absolute measured values after drying. The results are summarized in the following Table 3:
to , see footnotes at end of Table 1
Again the advantages of Polymer A are especially apparent at low concentrations when compared to Pensize 730.

Claims

Claims
1. A composition comprising a) from 0.1 to 30% by weight, based on the total weight of the composition, of a colouring pigment, b) from 0.1 to 20% by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch, the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally, iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20% by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to 100% by weight, based on the total weight of the composition.
2. A composition according to claim 1 , in which the colouring pigment is selected from pigments disclosed in the Colour Index International under the designations C.I. Pigment Yellows 1 to 221 , C.I. Pigment Oranges 1 to 81 , C.I. Pigment Reds 1 to 283, C.I. Pigment
Violets 1 to 53, C.I. Pigment Blues 1 to 81 , C.I. Pigment Greens 1 to 56, C.I. Pigment Browns 1 to 47 and C.I. Pigment Blacks 1 to 35.
3. A composition according to claim 1 or claim 2, wherein the starch/latex copolymer consists of i) from 5 to 50% by weight of starch and ii) from 50 to 95% by weight of the monomeric components.
4. A composition according to any one of claims 1 to 3, wherein the starch component of the copolymer, component b) of the composition, is a degraded, oxidized anionic starch.
5. A composition according to any one of claims 1 to 4, in which the starch/latex copolymer is obtained by copolymerization of i) from 20 to 40% by weight of styrene or a substituted styrene, ii) from 20 to 50% of an acrylate or a methacrylate and iii) from 5 to 20% by weight of one or more further ethylenically unsaturated monomers, in the presence of from 15 to 40% by weight of starch.
6. A composition according to any one of claims 1 to 5, in which the starch/latex copolymer is in the form of an aqueous dispersion having a dry content of from 20 to 50% by weight.
7. A composition according to any one of claims 1 to 6, wherein the auxiliary is selected from fixing agents, dispersants, binder resins, insolubilizing and/or cross linking agents, anionic, cationic and neutral polymers, wet-strength agents, antifoams and biocides.
8. Use of the composition according to any one of claims 1 to 7 for the surface colouration of paper.
9. A method for the surface colouration of paper by applying to the paper surface a composition comprising a) from 0.1 to 30% by weight, based on the total weight of the composition, of a colouring pigment, whereby the colouring pigment is in solid form or in the form of a dispersion, b) from 0.1 to 20% by weight, based on the total weight of the composition of a starch/latex copolymer, characterized in that, in addition to starch, the monomeric components that are copolymerized comprise i) styrene or a substituted styrene, ii) an acrylate and/or methacrylate and, optionally, iii) one or more further ethylenically unsaturated monomers, c) from 0 to 20% by weight, based on the total weight of the composition, of starch or a starch derivative, d) from 0 to 10% by weight, based on the total weight of the composition of one or more auxiliaries and e) water to complete to 100% by weight, based on the total weight of the composition.
10. Paper, which has been treated with a composition according to any one of claims 1 to 7 or by the method according to claim 9.
EP20070703929 2006-01-26 2007-01-17 A composition for surface colouration of paper Not-in-force EP1977041B1 (en)

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EP20070703929 EP1977041B1 (en) 2006-01-26 2007-01-17 A composition for surface colouration of paper
PCT/EP2007/050427 WO2007085553A1 (en) 2006-01-26 2007-01-17 A composition for surface colouration of paper

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JP5289013B2 (en) * 2007-12-17 2013-09-11 関西ペイント株式会社 Multilayer coating film forming method, multilayer coating film and coated article
FI122694B (en) 2008-12-18 2012-05-31 Kemira Oyj Process for improving rheological properties of aqueous pigment suspension and dispersant
FI124806B (en) * 2008-12-18 2015-01-30 Kemira Oyj Coating paste composition and paper or paperboard coated therewith
CN102115551A (en) * 2010-12-31 2011-07-06 永港伟方（北京）科技股份有限公司 Starch-based nano biological latex and preparation method thereof
EP3601662A1 (en) 2017-03-23 2020-02-05 Polytex Sportbeläge Produktions-GmbH Support mat for hybrid turf
EP3585935A1 (en) 2017-03-23 2020-01-01 Polytex Sportbeläge Produktions-GmbH Hybrid turf or artificial turf with inhomogeneous latex backing
EP3467203A1 (en) 2017-10-06 2019-04-10 Polytex Sportbeläge Produktions-GmbH Compostable turf with decomposition inhibitor
EP3636836A1 (en) 2018-10-09 2020-04-15 Polytex Sportbeläge Produktions-GmbH Method for improving sports flooring comprising natural grass

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3627594A1 (en) 1986-08-14 1988-02-18 Basf Ag SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS
DE3702712A1 (en) 1987-01-30 1988-08-11 Basf Ag SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS
DE3732981A1 (en) 1987-09-30 1989-04-13 Basf Ag METHOD FOR DYING PAPER
JPH0482993A (en) * 1990-07-16 1992-03-16 Sanyo Shikiso Kk Pigment dispersion for colored paper making
DE4229142A1 (en) 1992-09-01 1994-03-03 Basf Ag Paper sizing mixtures
DE19806745A1 (en) 1998-02-18 1999-08-19 Bayer Ag Aqueous polymer dispersion useful as surface sizing agent for paper, cardboard etc.
FI105565B (en) * 1999-02-05 2000-09-15 Raisio Chem Oy Polymer dispersion and process for its preparation
US20030005527A1 (en) * 2001-07-03 2003-01-09 Basf Corporation Thickeners for paper dye compositions
US20040110883A1 (en) * 2002-10-18 2004-06-10 Pakan Dwight J. Coloration of paper by binding colorants in a surface application
GB0308487D0 (en) * 2003-04-14 2003-05-21 Ciba Spec Chem Water Treat Ltd Paper coating compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007085553A1 *

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US20130276245A1 (en) 2013-10-24
JP5377979B2 (en) 2013-12-25
ATE465298T1 (en) 2010-05-15
CN101375001B (en) 2011-10-05
DE602007005979D1 (en) 2010-06-02
TW200734511A (en) 2007-09-16
AU2007209377B2 (en) 2011-02-24
EP1977041B1 (en) 2010-04-21
US20100285324A1 (en) 2010-11-11
WO2007085553A1 (en) 2007-08-02
TWI421391B (en) 2014-01-01
AU2007209377A1 (en) 2007-08-02
US8487022B2 (en) 2013-07-16
CN101375001A (en) 2009-02-25

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